Olefin polymerization catalyst composition and olefin polymerization process using the same

a technology of olefin polymerization and composition, which is applied in the direction of catalyst activation/preparation, physical/chemical process, chemical/physical process, etc., can solve the problems of high production cost of conventional metallocene catalyst and difficulty in easily controlling the properties of olefin polymers, and achieves excellent commercial availability, simple process, and the effect of minimizing the time and process for producing catalys

Inactive Publication Date: 2013-12-26
DAELIM IND CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0010]The olefin polymerization catalyst composition according to the present invention can exhibit various properties by appropriate selection and combination of the components thereof. Therefore, its commercial availability is excellent because olefin polymers having various properties can be made to order. The catalyst composition of the present invention can be produced by a simple process. Therefore, time and process for producing the catalyst can be minimized. And, the catalyst composition of the present invention has high polymerization activity which remains constant unlike existing catalysts whose polymerization activity decreases with polymerization time, so that its commercial productivity is excellent. In addition, by using the olefin polymerization process according to the present invention, the molecular weight, the molecular weight distribution, and the composition distribution of the produced olefin polymer or copolymer can be easily controlled in an uniform phase (solution) or a non-uniform phase (gas or slurry) polymerization process.

Problems solved by technology

However, the conventional metallocene catalyst has disadvantages of high production cost due to its synthetic process by several reaction steps under complicated reaction conditions, and difficulty in easily controlling properties of olefin polymers as necessary.

Method used

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  • Olefin polymerization catalyst composition and olefin polymerization process using the same
  • Olefin polymerization catalyst composition and olefin polymerization process using the same

Examples

Experimental program
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Effect test

example 1

Preparation of Catalyst and Solution Polymerization of Ethylene

[0034]In a 500 ml flask of nitrogen atmosphere, indenyl aluminium diethyl(Ind-AlEt2) 5.1 mg (0.018 mmol), bis(tetrahydroindenyl)zirconium dichloride 2.4 mg (Mw: 401, 0.006 mmol), zirconium chloride (ZrCl4) 1.4 mg (0.006 mmol) and methyl aluminoxane (MAO, Albemarle company, 10% toluene solution) 10 ml were mixed (Zr=6.0 μmol, Al / Zr mole ratio 2,500), and stirred at 60° C. for 30 minutes to obtain a catalyst solution.

[0035]A stainless autoclave reactor of 1 L having a jacket for supplying cooling water for controlling a polymerization temperature was purged with isobutane (one time) and ethylene (five times) at about 85° C. to remove impurities, and then cooled to room temperature. Dried hexane 300 ml and triisobutylaluminum (TIBA) as an impurity remover 1.0 mmol were added into the washed reactor at room temperature, and heated to a polymerization temperature of 70° C. The obtained catalyst solution was directly added int...

example 2

Preparation of Catalyst and Copolymerization of Ethylene / Hexene-1

[0036]In a 500 ml flask of nitrogen atmosphere, indenyl aluminium diethyl(Ind-AlEt2) 318 mg, bis(tetrahydroindenyl)zirconium dichloride 124 mg, zirconium chloride (ZrCl4) 69 mg and methyl aluminoxane (MAO, Albemarle company, 10% toluene solution) 50 ml were mixed, and stirred at 60° C. for 30 minutes to obtain a catalyst solution. 10 g of silica calcined at 220° C. was added to the produced catalyst solution, and ultrasonic wave was applied for 90 minutes, and the supernatant was discarded. The remaining solid particles were washed with hexane (1 time), and dried in vacuum to obtain a supported catalyst which was free-flowable solid powder.

[0037]A stainless autoclave reactor of 1 L having a jacket for supplying cooling water for controlling a polymerization temperature was purged with isobutane (one time) and ethylene (five times) at about 110° C. to remove impurities, and then cooled to 67° C. Isobutane 400 ml and tri...

example 3

Preparation of Catalyst and Copolymerization of Ethylene / Hexene-1

[0038]In a 500 ml flask of nitrogen atmosphere, indenyl lithium (Ind-Li) 75 mg, bis(tetrahydroindenyl)zirconium dichloride 124 mg, zirconium chloride (ZrCl4) 69 mg and methyl aluminoxane (MAO, Albemarle company, 10% toluene solution) 50 ml were mixed, and stirred at 60° C. for 90 minutes to obtain a catalyst solution. 10 g of silica calcined at 220° C. was added to the produced catalyst solution, and ultrasonic wave was applied for 90 minutes, and the supernatant was discarded. The remaining solid particles were washed with hexane (1 time), and dried in vacuum to obtain a supported catalyst of free-flowable solid powder. Except for using the catalyst 61 mg prepared in the above step, the polymerization was carried out for 3 hours in accordance with the polymerization method of Example 2 to obtain the polymer 327 g. The polymerization rate during 3 hours of the polymerization reaction was kept steady. The catalytic acti...

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Abstract

The olefin polymerization catalyst composition comprises an organometallic compound represented by Formula 1; an organic transition metal compound represented by Formula 2; an organic transition metal compound represented by Formula 3; and an aluminoxane.
(Cp′)lM1R1mR2n  Formula 1:
    • wherein M1 is an element selected from the group of elements of Group 1, 2, 12, 13 and 14, (Cp′) is a cyclic hydrocarbyl group of 5 to 30 carbon atoms having at least 2 conjugated double bonds, R1 and R2 are independently a hydrocarbyl group of 1 to 24 carbon atoms, l is an integer of 1 to the valence of M1, m and n are independently an integer of 0 to 2, and l+m+n is equal to the valence of M1,
(4HInd)2M2X2  Formula 2:
M2X4  Formula 3:
    • wherein in Formulas 2 and 3, (4HInd) is a group having tetrahydroindenyl nucleus, M2 is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X is a halogen atom.

Description

FIELD OF THE INVENTION[0001]This invention relates to an olefin polymerization catalyst composition, and more particularly, to an olefin polymerization catalyst composition which has superior polymerization activity, and can easily control a molecular weight, a molecular weight distribution and a composition distribution of the produced olefin polymer or copolymer, and an olefin polymerization process using the same.BACKGROUND OF THE INVENTION[0002]A polyolefin, especially an ethylene polymer or an ethylene / α-olefin copolymer has a superior impact strength, transparency and so on. To produce the above stated ethylene polymers, a metallocene catalyst system consisting of an organometallic compound (generally, metallocene) which has ligands such as a cyclopentadienyl group, an indenyl group, a cycloheptadienyl group, a fluorenyl group, and an activator such as aluminoxane has been used (see German Patent No. 3,007,725, U.S. Pat. Nos. 4,404,344, 4,874,880, 5,324,800, and so on). Recent...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08F4/6592C08F4/16
CPCC08F4/646C08F4/65925C08F210/16C08F2500/12
Inventor HONG, SAH-MUNCHOI, HYE-SUN
Owner DAELIM IND CO LTD
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